Herbicidal trifluoromethyl-1,3-phenylenediamine compounds

ABSTRACT

N,N&#39;&#39;Substituted-1,3-phenylenediamine compounds having a trifluoromethyl and a nitro group on the aromatic ring. The compounds are useful as herbicides.

United States Patent [191 Woods et al.

[4 1 Sept. 2, i975 Stone, Whittier; Cecil W. LeFevre, Anaheim, all ofCalif.

[73] Assignee: United States Borax & Chemical Corporation, Los Angeles,Calif.

22 Filed: July 2, 1973 21 Appl. No.: 376,085

Related US. Application Data [62] Division of Ser. No. 57,787, July 23,1970, Pat. No.

3,764,625, which is a division of Ser. No. 812,357, April 1, 1969, Pat.No. 3,617,250.

[52] US. Cl. 260/247.5 R; 260/239 E; 260/268 PH; 260/243 B; 260/293.79;260/326.85; 260/293.63; 260/246 B [51] Int. Cl. C07D 295/00 [58] Fieldof Search. 260/247.5 R, 268 PH, 293.79, 260/239 E, 243 B [56] ReferencesCited UNITED STATES PATENTS 3,257,190 6/1966 Soper 71/121 3,297,6821/1967 Kuhn 260/239 E Soper 260/577 Woods 260/570.5 P

Primary Examiner-Robert Gerstl Assistant ExaminerRichard D. KellyAttorney, Agent, or F irm-James R. Thornton 5 7 ABSTRACTN,NSubstituted-l ,3-phenylenediamine compounds having a trifluoromethyland a nitro group on the aromatic ring. The compounds are useful asherbicides.

7 Claims, No Drawings HERBICIDAL TRIFLUOROMETHYL-l ,S-PHENYLENEDIAMINECOMPOUNDS This is a division of application Ser. No. 57,787 filed July23, 1970, now US. Pat. No. 3,764,625 which in turn is a division of ourco-pending application, Ser. No. 812,357 filed Apr. 1, 1969 now US. Pat.No. 3,617,250.

This invention relates to novel trifluoromethyl-N- substitutedphenylenediamine compounds and their use as herbicides. There isprovided by this invention a class of N-substituted-l,3-phenylenediaminecompounds having both a nitro and trifluoromethyl substituent on thearomatic ring which have outstanding herbicidal activity.

The novel compounds of this invention can be defined by the formulawherein R and R are each selected from hydrogen, alkyl, alkenyl,alkynyl, aralkyl, and aryl and R and R are each selected from alkyl,alkenyl, alkynyl, aralkyl, and aryl. Also, R,R and/or R R can representa portion of a cyclic group such as an alkylene chain to form aheterocyclic group containing carbon atoms and optionally other atoms,such as nitrogen, oxygen and sulfur, in addition to the nitrogen atomwhich is the point of attachment to the aromatic ring.

For convenience in naming the compounds, the amino nitrogen adjacent tothe trifluoromethyl group is referred to as N. The amino nitrogenadjacent to the nitro group on the ring is referred to as N. Thus, thenitro substituent is in the 4-position of the aromatic ring and thetrifluoromethyl group is in the 6-position of the aromatic ring. It willbe noted from the above definition that each amino nitrogen must have atleast one substituent thereon, thereby excluding the unsubstituted amino(NI-l groups.

Typical examples of the groups represented by R R R and R, as definedabove are the lower alkyl, lower alkenyl and lower alkynyl groups havingup to about 8 carbon atoms, including the cyclic analogues thereof aswell as the halo, nitro, hydroxy and lower alkoxy substitutedderivatives thereof. Representative groups are methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-octyl,allyl, 2-butenyl, 2-butynyl, 3butynyl, crotyl, methylallyl, 2- pentynyl,2-hydroxyethyl, 2-methoxyethyl, 3- ethoxypropyl, Z-chloroallyl,2-bromoallyl, propargyl, 4-chloro-2-butenyl, 4-bromo-l-butenyl,3-iodo-2- pentenyl, 4-chloro-2-butynyl, 3-nitrobutyl, 2- nitroethyl,cyclohexyl, cyclopropyl, cyclobutyl, cyclohexenyl, and the like.

The substituents on the amino nitrogens according to this invention, canalso be an aralkyl or aryl group and especially the monocyclic aralkyland aryl groups such as benzyl, phenylethyl, phenyl, 2,4-dichlorophenyl,3- bromophenyl, 4-methoxyphenyl, methylphenyl, 4-nitrophenyl,2,4-dimethylphenyl, 3- fiuorophenyl, 4-chlorobenzyl, 2,4-dichlorobenzyl,and

6 3-chloro-4- 5 the like. Thus, the aralkyl and aryl groups can beunsubstituted or have nuclear substituents such as lower alkyl, loweralkoxy, halo and nitro.

Furthermore, R,R and/or R -R can represent a fragment of a ring of whichthe amino nitrogen is a part thereof, such as the piperdino, morpholino,thiomorpholino, piperazino, aziridinyl, and pyrrolidino rings. Suchheterocyclic ring groups have the structure A -N Z in which Z is analkylene, alkyleneoxy, alkyleneimino, or alkylenethio group having fromabout 2 to 6 carbon atoms in the chain.

A preferred class of compounds according to this invention are those inwhich R and R are each selected from hydrogen, alkyl of l to 5 carbonatoms including the halo-substituted derivatives thereof, and alkenyl of3 to 5 carbon atoms including the halo-substituted derivatives thereof;and R and R are each selected from alkyl of l to 5 carbon atoms,including the halosubstituted derivatives thereof, and alkenyl of 3 to 5carbon atoms including the halo-substituted derivatives thereof. Thus,representative preferred examples of R R R and R are methyl, ethyl,n-propyl, isopropyl, nbutyl, sec-butyl, sec-pentyl, 2-chloroethyl, 5-bromopentyl, allyl, Z-butenyl, 2-chloroallyl, 2- iodoallyl,3-bromo-2-pentenyl, 4-chloro-2-butenyl, and the like. i

The most preferred compounds are those in which the N and N groups aredifferent; that is, the two amino groups are unsymmetricallysubstituted. In this preferred class of compounds the total number ofcarbon atoms in the N group is l to 4 and the total number of carbonatoms in the N group is 2 to 6.

Representative examples of this most preferred class of compounds are N-allyl-N -ethyl-4-nitro-6-trifluoromethyl- 1 ,3-

phenylenediamine N -ethyl-N N -dimethyl-4-nitro-6-trifluoromethyl- 1,3-phenylenediamine N-ethy1-N ,N -diethyl-4-nitro-6-trifluoromethyll 3-phenylenediamine trifluoromethyl-l ,3-phenylenediamine trifluoromethyl-l,3-phenylenediamine N -ethyl-N 2-chloroallyl)-4-nitro-6-trifluoromethyl-l ,3-phenylenediamine N -methyl-N-sec-butyl-4-nitro-6-trifluoromethyl- 1 ,3-phenylenediamineN,N-diethyl-N -allyl-4-nitro-6-trifluoromethyll ,3-

phenylenediamine trifluoromethyll ,3-phenylenediamine N -methyl-N ,N-di-n-propyl-4-nitro-6- trifluoromethyl-l ,B-phenylenediamine N-methyl-N ,N -diethyl-4-nitro-6-trifluoromethyll ,3-phenylenediamine l,3-phenylenediamine The compounds of this invention are eithercrystalline solids or high boiling liquids. Generally they are onlyslightly soluble in water and are moderately soluble in the usualorganic solvents such as ethanol, ace- 3 4 tone, ether and benzene. Thecompounds are readily nitrobenzotrifluoride, 30 ml. of ethanol and 15ml. of prepared by reaction of one or two primary or secondliquidmethylamine. The reaction tube was sealed and ary amines with a2,4-dihalo--nitrobenzotrifluoride heated in a bath at 100C. for 184hours. The cooled according to the following equation: reaction tube wasthen opened and the contents evapo- NH R3\NH a 211x N R B in which X isa reactive halogen such as chlorine or 15 rated to dryness to give ayellow-brown solid. To the bromine and R R R and R, can have thesignifisolid was added 200 ml. of water to dissolve the methylcancepreviously assigned. amine hydrochloride and the water-insoluble productWhen R and R are the same as R and R,,, that is was separated therefromby filtration. After washing when the substituted N amino group is thesame as the the solid again with water, it was dissolved in 300 ml.

substituted N" amino group in the resultant product, of refluxing 95%ethanol. Upon cooling, the product the reaction takes place in one stepusing an excess, crystallized and was isolated by filtration, obtainingthat is, at least 4 moles of amine for each mole of 2,4- 3.64 grams(67%) of the desired product as a yellow,dihalo-5-nitrobenzotrifluoride. When R and R are difcrystalline solid,melting at 21 l212C.

ferent from R and R the reaction requires two steps in which a differentamine is employed in each step. In 25 EXAMPLE n the first step about 2moles of the amine forming the N N,N-diethyl-4-nitro-6-trif1uoromethyl-1,3-

group is reacted with about one mole of the 2,4-dihalophcnylenediamine pa d adjacent to the mtro subsmuent on the reaction of2,4-dichloro-5-nitrobenzotrifluoride with aromatlc g- In the Second Stepabout 2 moles of the ethylamine. The crystalline product was obtained asamine forming the N group is reacted with the yellow plates melting at 1o 165C monoamino-substituted compound to form the unsymmetricallysubstituted phenylenediamine compound. EXAMPLE In The second reactiontakes place preferably in a sealed N N bi (di th 1)-4 it 6 t ifl th l 13- reaction vessel, such as a sealed tube or an autoclave,phenylenediamine to avoid losses of amine and provide easy control ofthe This compound was prepared in a similar manner by reaction. In thecase of higher boiling amines it is not reaction of2,4-dichloro-5-n1trobenzotr1fluor1de with necessary to use a sealedreaction vessel for the reacdimethylamme. The crystalline product meltsat tion but it is sufficient merely to heat the reaction mixture in thepresence of a suitable solvent.

A reaction temperature of from about 50 to about EXAMPLES 125C.preferably is employed to give good yields of The following compoundswere prepared in a similar the desired product and a satisfactory rateof reaction, manner by reaction of 2,4-dichloro-S-nitrobenzotriboth inthe case of using a sealed reaction vessel and fluoride with thecorresponding amine. when the reactants are heated in the presence of a501- IV. N,N"-di-n-propyl-4-nitro-6-trifluoromethyl-1,3- vent. Hydrogenhalide is formed as a byproduct, and, phenylenediamine; m.p. 6364C. inthe presence of excess amine, is converted to the V. N,N-diisopropyl-4-nitro-6-trifluoromethyl-l,3- amine hydrohalide which canbe readily removed by phenylenediamine; m.p. l2l.5123C. washing withwater or by filtration after dissolution of VI. N,N-dicyclopropyl-4-nitro-6-trifluoromethyl-l,3- the product in a suitablesolvent. The desired products phenylenediamine; m.p. 156l57C. can bepurified by well known procedures such as by ,N y y recrystallization ordistiliation under reduced pressure. phenylenediamine; m.p. 7474.5C.

The intermediate 2,4-dihalo-5-nitrobenzotrif1uorides III- N,Ndi-n-butyl-4-nitro-6-trifluoromethyl-l,3- can be prepared by nitrationof the corresponding phenylenediamine, m.p. 5959.5C.2,4-dihalobenzotrifluoride such as described by French ;NS6Cbutyl-4-nitro-6-trifluoromethyl- 1 ,3- Pat. No. 745,293 (see Chem.Abstracts 27, 4414). ph ny min -p- 1 -l5 mm.

The following examples describe preparation of rep- X- N,N-diCyClOheXyl-4-nitr06-trifluoromethyll ,3 resentative compounds of thisinvention but it is to be phenylcnediamine; -l 7-5C. understood that theinvention is not to be limited to the 60 -d Zyl-nitr06-trifluoromethyl-1 ,3-

specific examples given. phenylenediamine; m.p. l20-l2lC EXAMPLE IEXAMPLE XlI v N ,N -di( p-methoxyphenyl )-4-nitro- 6-trifluoromethyl N,N"-dimethyl-4-nitro--trifluoromethyl-l ,3- 1,3-phenylenediaminephenylenedlamme 2,4-Dichl0ro-5-nitrobenzotrifluoride was reacted A heavywalled glass reaction tube of about 50 ml. with p-anisidine dissolved in1,2-dimethoxyethane in a capacity was charged with 5 grams of2,4-dichloro-5- sealed tube at 150C. for hours to give the desiredproduct melting at l9l192C., after recrystallization from ethanol.

EXAMPLE XIII N ,N-di-n-propyl-S -chloro-2-nitro-4-trifluoromethylaniline A heavy walled glass reaction tube ofapproximately 100 ml. capacity was charged with 35.0 grams (0.1346 mole)of 2,4-dichloro-5-nitrobenzotrifluoride, 27.24 grams (0.2692 mole) ofdi-npropylamine and 60 ml. of ethanol. The tube was sealed and heated ina bath at 100C. for 4 days. The cooled reaction mixture was thenevaporated to dryness to give a residue which was extracted with boilingdiethyl ether. The insoluble di-npropylamine hydrochloride was removedby filtration and washedwith additional ether. The combined etherfiltrates were evaporated to give a liquid residue which was distilledunder reduced pressure to give 42 grams of the product as an orangeliquid, b.p. 107118C./0.15 mm.; n 1.5359.

N-ethyl-N ,N -di-npropyl-4-nitro-6-trifluoromethyI- l,3-phenylenediamine A glass reaction tube was charged with 0.013 mole ofN,Ndi-n-propyl-5-chloro-2-nitro-4- trifluoromethylaniline, 0.0536 moleof ethylamine and 20 ml. of ethanol. The tube was sealed and heated in abath at 100C. for 140 hours. The contents of the tube were cooled andthe ethanol removed by evaporation. The residue was extracted with hotether and the insoluble amine hydrochloride separated by filtration. Theether filtrate was evaporated to give an oily residue which wasdistilled under reduced pressure to give the desired product at132134.5C./0.1

EXAMPLE XIV N,N-diethyleneoxy-5-chloro-2-nitro-4- trifluoromethylanilineA solution of 8 grams (0.0308 mole) of 2,4-dichloro-S-nitrobenzotrifluoride and 5.9 grams (0.0677 mole) of morpholine in 35ml. of ethanol was refluxed for 18 hours. The solvent and excessmorpholine were removed under reduced pressure to give a solid residue.The residue was extracted with water and the waterinsoluble materialrecrystallized from aqueous ethanol to give 8.63 grams (70%) of productmelting at 9899.5C.

N -ethyl-N,N*-diethyleneoxy-4-nitro--trifluoromethyl-l.B-phenylenediamine trifluoromethyl-l ,3-phenylenediamine; b.p.140-148C./O.2 mm.

N ,N -dimethyl-N ,N -diisopropyl-4-nitro-6- trifluoromethyl-l,3-phenylenediamine; m.p.

9293C. N -ethyl-N -tcrt-butyl-4-nitro-6-trifluoromethyl-l ,3-

phenylenediamine; m.p. 149150C. N-n-propyl-N-a1lyl-4-nitro-6-trifluoromethyll ,3-

phenylenediamine; m.p. 70.571.5C. N-ethyl-N-allyl4-nitro-6-trifluoromethyll ,3-

phenylenediamine; m.p. 95.596.5C. N-methyl-N ,N -di-n-propyl-4-nitro-6-trifluoromethyl-l ,3-phenylenediamine; 76.577.5C. N -ethyl-N ,N-dimethyl-4-nitro-6-trifiuoromethyl- 1,3-phenylenediamine; m.p. 10lC. N-allyl-N -ethy1-4-nitro-6-trifluoromethyl-1,3-

phenylenediamine; m.p. l0l102C. N-methyl-N-sec-butyl-4-nitro-6-trifluoromethyl- 1,3-phenylenediamine; m.p. 9596C.N -methyl-N ,N -diethyl-4-nitro-6-trifluoromethyl- 1,3-phenylenediamine;m.p. 68-69C. N -ethy1-l\I 2-chloroallyl )-4-nitro-6-trifluoromethyl- 1,3-phenylenediamine; m.p. 78-8 1C. N-ethyl-N 2-methoxyethyl )-4-nitro-6-trifluoromethyll ,3-phenylenediamine; I29.5-l30.5C. N -ethyl-N-n-octyl-4-nitro-6-trifluoromethyll ,3-

phenylenediamine; m.p. 4142C. N-ethyl-N ,N-di(2-methoxyethyl)-4-nitro-6- trifluoromethyl- 1 ,3-phenylenediamine;l64.5l65C./O.35 mm. N-ethyl-N -benzyl-4-nitro-6-trifluoromethyl-l ,3-

phenylenediamine; m.p. 9798C. Nn-propyl-N",N-diethy1-4-nitro-6-trifluoromethyl- 1,3-pher1ylenediamine; b.p. l34l 38C./0.- 150.20 mm. N-ethyl-N -propargy1-4-nitro-6 trifluoromethyll ,3-

phenylenediamine; m.p. 160.5161.5C. N-methyl-N -ethyl-N-n-butyl-4-nitro-6- trifluoromethyl-l ,3-phenylenediamine; l43l57C./O.18-020 mm. N-ethyl-N -phenyl-4-nitro-6-trifluoromethyl-l ,3-

phenylenediamine; m.p. 94-94.5C. N-ethyl-N,N -tetramethylene-4-nitro-6-trifluoromethyl-l ,3-phenylenediamine; 1 30-l 3 1C. N -sec-butyl-N ,N-diethyl-4-nitro-6-trifluoromethyl- 1,3-phenylenediamine; b.p. 136C./0.-14-015 mm. N'-n-propyl-N -ethyl-4-nitro-6-trifluoromethyl- 1 ,3-

phenylenediamine; m.p. 808 1C. N -n-propyl-Nisopropyl-4-nitro-6-trifluoromethyl- 1,3-phenylenediamine; m.p.73.574.5C. N,N-dimethyl-N ,N -di-n-propyl-4-nitro-6- trifluoromethyl-l,3-phenylenediamine; l27l 32C./0. 14 mm.

N N -dimethyl-N-n-propyl-4-nitro-6- trifluoromethyl-l,3-phenylenediamine; m.p. 47-48C.

N"-di-n-propyl-4-nitro-6- N-n-propyl-N trifluoromethyll,3-phenylenediamine; l43l 5lC./O. l 8 mm.

N -allyl-N", N -diethyl-4-nitro-6-trifluoromethyl-l ,3-

The compounds can be applied as both a preemergence or a post-emergencetreatment; that is they can be applied to soil in which the weeds willgrow or they can be used to kill or suppress the growth of weeds or tokill or prevent the emergence of seedlings of undesirable plants. Thus,the compounds can be used to control the growth of weeds by applying aphytotoxic amount of one or more of the active compounds of thisinvention to the locus to be protected, that is, soil in which the weedsare growing or will grow or the foliage of the growing plants. Weeds" asused herein is meant to include any plant growth which is undesirable.

Generally an application rate of from about 0.1 to about 25 pounds ofone or more of the active com- Phenylenediamlne; -P- 15 pounds per acreis effective in controlling plant growth. Preferably an application rateof from about 0.5 to Y y about 5 pounds per acre is employed. At suchrates the trlfluoromethyll3'Pheny1ened1amme -P' undesirable weeds arekilled or stunted with little or no l35C./O.l2 mminjury to desirablecrops. The Compounds of thls Invention are excellent herbl' 20 Thefollowing examples illustrate the herbicidal accides and are especiallyuseful as selective herbicides i i f i l compounds f hi invention forcontrolling weeds in the presence of desirable crops especially thegrassy weeds such as, for example, fox- EXAMPLE XV tall, water grass,and crabgrass. Many of the compounds of this invention may be used incontrolling weeds in desirable grassy crops such as corn and rice, Thcompounds to be tested were evaluated as preas well as the small grains,and also the broad leaf crops m rg e herbicides on a broad class ofrepresenta- Such as cotton and Soy beans- A150, of the P tive weeds andcrops. Greenhouse flats were planted to ferred compounds are effectivein controlling wild oats i ed, cheat, wild oats, foxtail, morning glory,water which constitute a major problem in small grain crops grass, isugar b et cotton, corn, barley, and soy such as wheat and barley. Theirutility in controlling beans, On the same day of planting, the flatswere weeds in grassy crops such as corn, rice, and grains is sprayedwith an ethanol solution of the compound to be surprising and unexpectedin view of the phytotoxicity tested at a rate of one pound per acre. Theflats were of many other aromatic amine derivatives to such k t i theeenh use and watered when needed. grassy crops. It has also been fountha he p cifi Twenty-two days after treatment, the plants wereevalphenylenediamines of this invention are much less voluated forherbicidal activity and rated on a O to 9 scale atile than many othersubstituted aromatic amines and in which 0 no effect; 5 substantialinjury with slight will move better in the soil, as well as possessingbetter kill and 9 complete kill. The following results were ultravioletstability. 40 obtained:

TABLE I Compound Activity* (NTP 4-nitro-6-trifluoromethyl-Lil- P CH WO FM W R SB CO CR B SO phcnylencdiamine) N'-ethyl-N-scc-butyl- NTP 4 2 9 90 7 0 3 o 2 0 0 N'n-pr0pyl-N-secbutyl-NTP 8 0 9 9 0 7 0 2 0 4 1 0N,N-dimcthyl-N"-scchutyl-NTP 4 2 9 9 e 7 0 4 0 7 1 0 N',N-di-sec-butylNTP 206705000000 N,N-dimcthyl-N,N-

diethyl-NTP 8 3 9 9 1 5 0 4 0 4 0 0 N-n-propyl-N".N-

diethyl-NTP 4 0 1 4 2 5 0 3 0 4 0 0 N'-allyl-N,N"-dicthyl- NTP 6 1 9 8 1s 0 3 0 0 0 0 N -cthyl-N,N"-di( 2- methoxyethyU-NTP 2 0 5 4 0 4 0 0 0 00 0 N-cthyl N",N-tctramethylene-NTP 4 l l 8 0 4 0 l O 0 0 0N-sec-butyl-N-cthyl- NTP 415817030300 N'-mcthyl-N"-ethyl- NTP63590804l400 N-mcthyl-N"-isopropyl-NTP 4 0 5 8 0 4 0 1 0 2 0 0N'.N'-dimethyl-N" npropyl-NTP Table 1- Continued Compound Activity* (NTP4-nitro-6-trifluoromethyl-l ,3- P CH W0 F M W R SB CO CR- B SOphenylenediamine) N-n-propyl-N"-ethyl NTP 4 l 6 9 O 4 0 l 0 4 0 ON-n-pr0pyl-N",N-din-propyl-NTP 4 2 s 9 3 8 0 0 1 4 0 o "P pigweed R riceCH cheat SB sugar beets W0 wild oats CO cotton F foxtail CR corn Mmorning glory B barley W water grass S0 soy beans EXAMPLE XVI Thecompounds to be tested wereevaluated as both a pre-emergence andpost-emergence treatment on a broad class of weeds and crops. Greenhouseflats were planted to the species tested in Example XV and the flatssprayed on the same day of planting with an ethanol solution of thecompound to be tested at a rate 0 2 pounds per acre.

Another set of flats with the same plants was treated after the plantshad emerged and were about 1 inch in EXAMPLE XVII Greenhouse flats wereplanted to cheat, wild oats, foxtail, water grass, crabgrass, andmillet. On the same day of planting the flats were sprayed with anethanoldioxane solution of the compound to be tested at a rate of 25pounds per acre. The flats were kept in the greenhouse and watered asneeded. Twenty-one days after treatment the flats were evaluated andrated as described in Example XV. The following results we're obtained:

*' applied at 22 pounds per acre height. These flats were also sprayedwith an ethanol solution of the compound at a rate of 2 pounds per acrein order to determine post-emergence activity. The

flats were kept in the greenhouse and watered when needed. Twenty-twodays after treatment, the flats were evaluated and rated as described inExample XV. The following results were obtained:

TABLE II Compound A Compound B Post Pre Post Compound C Plant SpeciesPre Pre Post Pigwced Cheat Wild oats Foxtuil Morning glory Water grassRice Sugar bccts Cotton Corn Barley Soy bean ccz caocaccwol CCNWBUIAMUCJK lccJ-scwcochccuq CWNUIC\IWUIWC-P rucecowoeccocc ccawqcwwx u-oCompound A N -methyl-N.N di-n-prupyl-4-nitro-(Hrifluommcthyb l.B-phenylcnediamine Compound B N-methylN"-sec-hutyl-4-nitro-6-trifluoromethyl-l ,Il-phenylenediamine Compound CN-mcthyl-N '.N diethyl-knitro-fi-trilluoromethyll ,J-phenylenediamineEXAMPLE XVIII N, N -Di(p-methoxyphenyl)-4-nitro-6-trifluoromethyl-1,3-phenylenediamine was applied as a pre-emergencetreatment at a rate of 15 pounds per acre to crabgrass, mustard andcucumbers. Twenty-six days after treatment the crabgrass showedsubstantial injury while the broad-leaf mustard and cucumbers showed noinjury.

EXAMPLE XIX Greenhouse flats were planted to millet, oats, soy beans,velvetleaf, sorghum, cheat, pigweed, water grass, crabgrass, foxtail,Johnson grass and ryegrass. On the same day as planting the flats weresprayed with an ethanol-dioxane solution of the compound to be tested ata rate of 5 pounds per acre. The flats were kept in the greenhouse andwatered when needed. Twenty-one days after treatment the flats wereevaluated and the herbicidal activity rated as described in Example XV.The following results were obtained:

TABLE lV Compound Activity* (NTP 4-nitro-6-trifluoromethyll 33- Ml SO V50 CH P W CB F JG RY phenylenediamine) N-cthyl-N",N-di(2-methoxyethyl)-NTP 9 4 0 0 4 l 9 9 9 9 9 8 N'-ethyl-N,N-diethylencoxy-NTP3 0 O 0 l) 0 l 3 0 3 2 0 N'-ethyl-N-(2-chloroaIlyl)-NTP 9 3 0 0 4 0 8 79 8 8 3 *MI millet S0 sorghum CB crabgrass O oats CH cheat F foxtail S0soy beans P pigweed JG Johnson grass V velvetleaf W water grass RYrycgrass EXAMPLE XX Greenhouse flats were planted to pigweed, crabgrass,wild oats, giant foxtail, sorghum, water grass, rice,

the same day as planting, the flats were sprayed with an ethanolsolution of the compound to be tested at a rate of 1 pound per acre. Theflats were kept in the greenhouse and watered when needed. Nineteen daysafter Johnson grass, cotton, corn, barley and soy beans. On

treatment the flats were evaluated and the herbicidal activity rated asdescribed in Example XV. The following results were obtained:

TABLE V Compound Activity* (NTP 4-nitro-6-trifluoromethyl-L3- P CB W0 FW R JG CO CR B SO phenylenediaminc) N,N"-diethyl-NTP 7 9 3 9 4 8 0 8 0 00 l N,N"-diisopropyl-NTP 1 3 1 s 0 3 0 4 0 0 0 0 N.N-diallylNTP 3 7 4 83 8 0 6 0 0 0 0 N',N"-dicyclopropyl NTP 0 6 0 6 O 2 0 3 O O 0 0N,N-di-nropyl-NTP 7 8 3 8 4 6 0 5 0 O O O N'-ethyl-N-allyl-NTP 5 8 2 8 27 0 6 0 0 l 0 N-ethyl-N",N"-diethylpropyl-NTP 7 8 8 8 4 8 O 8 O 0 0 ON-ethyl-N-Phenyl-NTP 0 5 5 4 0 2 0 2 0 0 0 1 *P pigweed R rice CEcrabgrass JG Johnson grass W0 wild oats CO cotton F foxtail CR corn SGsorghum B barley Since a relatively small amount of one or more of the50 pended in a liquid carrier such as water, kerosene, alcohols, dieseloil, xylene, benzene, glycols, ketones, and the like. A surfactantpreferably is included to aid in dispersion, emulsification andcoverage. The surfactant can be ionic or nonionic, and may be liquid ora solid.

The use of the term surfactant herein is intended to include suchcompounds commonly referred to as wetting agents, dispersing agents andemulsifying agents.

Concentrated compositions containing the active agent which can besubsequently diluted, as with water, to the desired concentration forapplication to plants and soil are also provided. The advantages of suchconcentrates are that they are prepared by the manufacturer in a formsuch that the user need only mix them with a locally available carrier,preferably water, thereby keeping shipping costs to a minimum whileproviding a product which can be used with a minimum of equipment andeffort. Such concentrates may contain from about 5 to about 99% byweight of one or more of the active l,3-phenylenediamines with a carrieror diluent, which may be a solid or liquid. Liquid carriers which aremiscible with the active agent or other liquids in which the compoundmay be suspended or dispersed can be used. A surfactant is alsogenerally included to facilitate such dilution or dispersion in wa- 13ter. However, the surfactant itself may comprise the carrier in suchconcentrates.

The herbicidal compositions can include other beneficial adjuvants, suchas humectants, oils and contact agents. Also other herbicides, such asthe sodium borates, sodium chlorate, chlorophenoxyacetic acids,substituted uracils and ureas, carbamates, amides, and haloalkanoicacids, can be included in the formulation.

The following examples are presented to illustrate the preparation ofsuitable herbicidal compositions of this invention.

EXAMPLE XXI N,N -diethyl-4-nitro-6-trifluoromethyll ,3-

phenylenediamine (powdered) 95% Granular clay A granular formulation canbe prepared by dry blending the above constituents until uniformly mixedin a rotary mixer. A fine spray of water is sprayed onto the mixture,while tumbling, to adhere the compound to the clay. The material is thenair dried while tumbling to give a granular formulation which can beapplied to the soil or vegetation by hand or by a mechanical spreader.

EXAMPLE XXII 85% N -methyl-N,N -di-n-propyl-4-nitro-6-trifluoromethyl-1,3-phenylenendiamine 14% Bentonite clay 1% Sodiumlauryl sulfate surfactant A wettable powder formulation can be preparedby micronizing the 1,3-phenylenediamine and mixing uniformly withpowdered Bentonite clay and powdered sodium lauryl sulfate. The wettablepowder can be added to water or hydrocarbon oil and mechanicallyagitated to insure a uniform dispersion which can be sprayed withconventional equipment onto soil or vegetation.

EXAMPLE XXIII 25% N -methyl-N -sec-butyl-4-nitro-6-trifluoromethyl-l,3-phenylenediamine 5% Aromatic sulfonate surfactant 14% Chlorobenzene56% Methyl isobutyl ketone The 1,3-phenylenediamine is dissolved in amixture of Chlorobenzene and the ketone to form a concen tratedsolution. The emulsifying agent is then dissolved and a liquidformulation of an emulsifiable concentrate is obtained. The emulsifiableconcentrate can be added to water to dilute it to a desiredconcentration, and then sprayed with conventional equipment onto soil orvegetation.

Various changes and modifications of the invention can be made and, tothe extent that such variations incorporate the spirit of thisinvention, they are intended to be included within the scope of theappended claims.

What is claimed is:

1. A compound of the formula )JFES R RglkRu 14 where R and R are eachselected from hydrogen, lower alkyl, lower alkenyl, lower alkynyl,monocyclic aralkyl, and monocyclic aryl, and R and R are each selectedfrom lower alkyl, lower alkenyl, lower alkynyl, monocyclic aralkyl, andmonocyclic aryl, wherein at least one of said R R. l J and -N groupsrepresents A N z which is a cyclic group selected from piperidino,morpholino, thiomorpholino, piperazino, aziridinyl and pyrrolidino.

2. A compound according to claim 1 in which is represented by said and Ris selected from hydrogen, alkyl of l to 5 carbon atoms, alkenyl of 3 to5 carbon atoms, and the halo substituted derivatives thereof and R isselected from alkyl of 1 to 5 carbon atoms, alkenyl of 3 to 5 carbonatoms, and the halo-substituted derivatives thereof. 3. A compoundaccording to claim 1 in which is represented by said UNITED STATESPATENT OFFICE QERTIFICATE 0F CORRECTION Patent No. 9 5 Dated ptember 2,1975 Inventor(s) William G. Woods, Don L. Hunter, James D. Stone CecilW. LeFevre It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

In Column 11, line #9, TABLE V add--W water grass S0 soy beans-- Signedand Sealed this Arrest:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner of Parentsand Trademarks

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 in which3. A compound according to claim 1 in which
 4. The compound according toclaim 1,N1-ethyl-N3,N3-diethyleneoxy-4-nitro-6-trifluoromethyl-1,3-phenylenediamine.5. The compound according to claim 1,N1-methyl-N3,N3-pentamethylene-4-nitro-6-trifluoromethyl-1,3-phenylenediamine.
 6. The compound according to claim 1,N1-ethyl-N3,N3-(diethylene-(N-methyl)imino)-4-nitro-6-trifluoromethyl-1,3-phenylenediamine.
 7. The compound according to claim 1,N1-ethyl-N3,N3-tetramethylene-4-nitro-6-trifluoromethyl-1,3-phenylenediamine.